10524
I. Amurrio et al. / Tetrahedron 60 (2004) 10521–10524
O), 6.38 (dd, 1H, 3JZ3.4, 1.7 Hz, CH, Furyl), 6.62 (dd, 1H,
3JZ3.4 Hz, 4JZ0.7 Hz, CH, Furyl), 7.40 (dd, 1H, 3JZ
1.7 Hz, 4JZ0.7 Hz, CH–O, Furyl) ppm. Anal. calcd for
C17H31NO3Si2: C, 57.74; H, 8.84; N, 3.96. Found: C, 57.73;
H, 8.79; N, 3.89.
Acknowledgements
Financial support of this work by the Ministerio de
´
Educacionn, Cultura y Deporte, Project BQU2003-04967
is gratefully acknowledged.
4.2.5. 3-(tert-Butyldimethylsilyloxy)-2-(thiazol-2-yl)-2-
trimethylsilyloxybutyronitrile, 4e. [a]2D0ZC33.6 (cZ
1.2, CHCl3) (diastereomeric mixture 4e-I:4e-IIZ
95:5).Data for 4e-I, 1H NMR: (CDCl3, 300 MHz) d
K0.01 (s, 3H, CH3–Si, TBS), 0.05 (s, 3H, CH3–Si, TBS),
0.18 (s, 9H, 3!CH3–Si, TMS), 0.88 (s, 9H, tBu, TBS), 1.16
References and notes
3
3
1. For recent reviews, see: (a) Gregory, R. J. H. Chem. Rev. 1999,
99, 3649. (b) North, M. Tetrahedron: Asymmetry 2003, 14,
147.
(d, 3H, JZ6.1 Hz, CH3–CH), 4.17 (q, 1H, JZ6.1 Hz,
CH–O), 7.39 (d, 1H, 3JZ3.2 Hz, CH–S, Thiazolyl), 7.82 (d,
1H, 3JZ3.2 Hz, CH–N, Thiazolyl) ppm; 13C NMR:
(CDCl3, 75 MHz) d K4.38 (2!CH3–Si, TBS), 1.19 (3!
CH3–Si, TMS), 18.36 (Si–C–(CH3)3), 18.94 (CH3–CH),
2. Groutas, W. C.; Felker, D. Synthesis 1980, 861.
3. See Ref. 1 and: (a) Saravanan, P.; Anand, R. V.; Singh,
V. K. Tetrahedron Lett. 1998, 39, 3823. (b) Somanathan,
R.; Rivero, I. A.; Gama, A.; Ochoa, A.; Aguirre, G. Synth.
Commun. 1998, 28, 2043. (c) Jenner, G. Tetrahedron Lett.
1999, 40, 491. (d) Ward, D. E.; Hrapechak, M.; Sales, M.
Org. Lett. 2000, 2, 57. (e) Kantam, M. L.; Sreekanth, P.;
Santhi, P. L. Green Chem. 2000, 2, 47. (f) Wang, Z. G.;
Fetterly, B.; Verkade, J. G. J. Organomet. Chem. 2002, 646,
16. (g) Yadav, J. S.; Reddy, M. S.; Prasad, A. R. Tetrahedron
Lett. 2002, 43, 9703. (h) Azizi, N.; Saidi, M. R. J. Organomet.
Chem. 2003, 688, 283. (i) Lundgren, S.; Lutsenko, S.; Jonsson,
C.; Moberg, C. Org. Lett. 2003, 5, 3663. (j) Baleizao, C.;
Grigante, B.; Garna, H.; Corma, A. J. Catal. 2003, 215, 199.
(k) Kim, J. H.; Kim, G. J. Catal. Lett. 2004, 92, 123.
4. See: (a) Golinski, M.; Brock, C. P.; Watt, D. S. J. Org. Chem.
1993, 58, 159. (b) Bandini, M.; Cozzi, P. B.; Melchiorre, P.;
Umani-Ronchi, A. Tetrahedron Lett. 2001, 42, 3041. (c)
Wilkinson, S. H.; Grover, P. T.; Vandenbossche, C. P.; Bakale,
R. P.; Bhongle, N. N.; Wald, S. A.; Senanayake, C. H. Org.
Lett. 2001, 3, 553. (d) Bandini, M.; Cozzi, P. G.; Garelli, A.;
Melchiorre, P.; Umani-Ronchi, A. Eur. J. Org. Chem. 2002,
3243. (e) Yadav, J. S.; Reddy, B. V. S.; Reddi, M. S.; Prasad,
A. R. Tetrahedron Lett. 2002, 43, 9703. (f) Kim, S. S.; Kim,
D. W.; Rajagopal, G. Synthesis 2004, 213 and references cited
therein.
t
26.05 (3!CH3, Bu, TBS), 68.78 (CH–O), 77.85 (O–C–
CN), 118.19 (CN), 121.04 (CH–S, Thiazolyl), 143.32 (CH–N,
1
Thiazolyl), 168.91 (C, Thiazolyl) ppm. Data for 4e-II: H
NMR: (CDCl3, 300 MHz) d K0.08 (s, 3H, CH3–Si, TBS),
0.08 (s, 3H, CH3–Si, TBS), 0.18 (s, 9H, 3!CH3–Si, TMS),
0.83 (s, 9H, tBu, TBS), 1.25 (d, 3H, 3JZ6.1 Hz, CH3–CH),
3
3
4.32 (q, 1H, JZ6.1 Hz, CH–O), 7.39 (d, 1H, JZ3.2 Hz,
CH–S, Thiazolyl), 7.82 (d, 1H, 3JZ3.2 Hz, CH–N,
Thiazolyl) ppm. Anal. calcd for C16H30N2O2SSi2: C,
51.85; H, 8.16; N, 7.56. Found: C, 51.59; H, 8.16; N, 7.58.
4.2.6. (2R,3S)-2,3-Dihydroxy-2-(2-methoxyphenyl)bu-
1
tyro-nitrile, 5. [a]D20ZK5.3 (cZ2.3, CHCl3), H NMR:
3
(CDCl3, 200 MHz) d 1.28 (d, 3H, JZ6.6 Hz, CH3–CH),
2.72 (d, 1H, 3JZ4.4 Hz, HO–CH), 3.95 (s, 3H, OCH3), 4.30
(m, 1H, CH–O), 4.63 (s, 1H, HO–C–CN), 7.00 (d, 1H, 3JZ
3
8.3 Hz, CHAr–C–OCH3), 7.08 (t, 1H, JZ7.9 Hz, CHAr),
3
7.39 (td, 1H, JZ7.9 Hz, 4JZ1.7 Hz, CHAr), 7.60 (dd, 1H,
4
3JZ7.7 Hz, JZ1.7 Hz, CHAr) ppm; 13C NMR: (CDCl3,
75 MHz) d 18.11 (CH3–CH), 56.28 (OCH3), 71.80 (CH–O),
79.91 (O–C–CN), 112.35 (CHAr–C–OCH3), 118.94 (CN),
121.90 (CHAr), 124.29 (CAr), 128.79 (CHAr), 131.28 (CHAr),
156.74 (CAr–OCH3) ppm. Anal. calcd for C11H13NO3: C,
63.76; H, 6.32; N, 6.76. Found: C, 63.98; H, 6.39; N, 6.81.
´
5. Cordoba, R.; Plumet, J. Tetrahedron Lett. 2003, 44, 6157.
4.2.7. (4R,5S)-4-Cyano-4-(2-methoxyphenyl)-2,2,5-tri-
methyl-1,3-dioxolane, 6. [a]2D0ZK2.1 (cZ1.4, CHCl3),
1H NMR: (CDCl3, 300 MHz) d 1.52 (s, 3H, CH3, CK2),
1.66 (d, 3H, 3JZ6.2 Hz, CH3–CH), 1.72 (s, 3H, CH3, C-2),
6. To the best of our knowledge, only an isolated report
describing the use of Bu4NCN as catalytic agent for the
cyanosilylation of 3-pentanone (84% yield) has been pre-
viously reported. See: Evans, D. A.; Truesdale, L. K.
Tetrahedron Lett. 1973, 14, 4929.
3
3.92 (s, 3H, OCH3), 4.16 (q, 1H, JZ6.2 Hz, CH–O), 6.98
(d, 1H, 3JZ8.2 Hz, CHAr–C–OCH3), 7.15 (t, 1H, 3JZ
7.8 Hz, CHAr), 7.38 (td, 1H, 3JZ7.8 Hz, 4JZ1.6 Hz, CHAr),
7.63 (dd, 1H, 3JZ8.1 Hz, 4JZ1.6 Hz, CHAr) ppm; 13C
NMR: (CDCl3, 75 MHz) d 16.81 (CH3–CH), 26.53 (CH3,
CK2), 27.78 (CH3, C-2), 55.87 (OCH3), 80.73 (O–C–CN),
81.17 (CH–O), 111.18 (O–C–O), 112.24 (CHAr–C–OCH3),
118.36 (CN), 121.44 (CHAr), 123.80 (CAr), 126.96 (CHAr),
131.09 (CHAr), 156.87 (CAr–OCH3) ppm. Anal. calcd for
C14H17NO3: C, 68.00; H, 6.93; N, 5.66. Found: C, 67.84; H,
6.90; N, 5.68.
7. Stammen, B.; Berlage, U.; Kindermann, R.; Kaiser, M.;
Gunther, B.; Sheldrick, W. S.; Welzel, P.; Roth, W. R. J. Org.
Chem. 1992, 57, 6566.
8. Dondoni, A.; Fantin, G.; Fogagnolo, H.; Pedrini, P. Tetra-
hedron 1989, 45, 5141.
9. Chuit, C.; Corriu, R. J. P.; Reye, C.; Young, J. C. Chem. Rev.
1993, 93, 1371.
10. Reetz, M. Angew. Chem., Int. Ed. 1984, 23, 556.